NEW COMPOUNDS
2272
Vol. 67
TARLE I ALKYLSALICYLATES
n. p."0c.a or m. p.,
Yield,
%
145-147 (16 uim.)
04
167-168 (12mm.) 172-173 (I3 mm.) 139-141 (0.08mm ) 158-163 (0.08 mm.) 25
93 55 61 70
40.5
50 88 85
43-44
53 189-1!)0 (21 mm ) 145 (10 mm.) 152 (IO mm.)
ti7 b4
8s
-Analyses, %bCarbon Hydrogen De- M. p., %N Formula Calcd. Found Celcd. Found dv.* OC. FOrmUla Calcd. Found 1.5130 CiiHi40: 68.04 68.17 7.22 7.2Qd A 85 CisHaNiOa 7.22 6 . M e B' 59.5-60 CtiHirNiOI 1.5019 CuH190a 70.27 70.02 8.11 7.44 1.4983 CirHrrOi 72.00 71.132 8.80 9.14 A 45 CitHwNiG 6.30 6.49n 1.4937 CnHiaOi 73.38 i3.23 9.36 9.28 CisHacOi 74.51 74.88 9.81 9.70 A 42 CiiHnNsOl 6.60 5.57h B 45.5-46 CvHmNaOI 7.07 7.12 CitHirOa 75.45 75.10 10.17 10.42 B 52-53 CeHasNaCh 6.60 7.01 CzrHdh 76.24 76.01 10.50 9.98 B 50-51 CliHirNOl' 3.27 3.44 CPLH~ZOI 76.92 77.26 10.77 11.06 B 66.5-67 CnbHrNaO, 5.83 5.52 I . f j O l & CiaHarOr 72.00 71.45 8.80 8.41 A 95 C17HuNa0n 7.18 6.971 1.5227 ciOI&?04 61.22 60.80 6.12 6.15 1.5157 CiiHidO4 62.86 61.6s 6.67 6 . 0 9 D'I?
a All melting points and boiling points are uncorrected. Microanalyses are by Misses P. Curraii and A. Rainey. A E 3,s-Dinitrobenzoate; B = 3,5-dinitro. This is a previously reported compound; see Sah and Ma (ref. 1) and also Croxall, Sowa and Nieuwland, J . Org. Chem., 2, 253 (1937). e %C, calcd.: 55.67; found: 55.92; %H, calcd.: 4.12, found: 4.16. f Prepared and atmlyzed by Sah and Ma (ref. 1). 0 %C, calcd.: 59.46; found: 59.21; %a,calcd.: 5.41; found: 4.69. * %C, calcd.: 62.40; found: 62.34; %H, calcd.: 6.40; found: 6.08. ' The mononitro derivative %C, calcd.: 52.31; fouud: 51.78;. %H, calcd.: 3.59: found: 3.35. was obtained with this ester. . 0
J
homologs. The esters and derivatives prepared are listed chloride [McCombie and Purdie, J . Chem. Soc. 1217 (I935)] for three hours. After filtration of the potassium in Table I. The esters were all prepared by standard procedures, chloride (theoretical quantity) the alcoholic filtrate was the actual conditions used for each one being deteriniiied evaporated under 10 mm., the residue was taken up in by the boiling poii?t and water-solubility of the alcohol water, thrice extracted with ether and the ether solution dried with magnesium sulfate. Distillation a t 134-13: O being used. 12 mm. yielded 2.80 g. (66%) of triethoxytriethylRESEARCH LABORATORIES FREEMA& H. MICMILLAVunder amine, d2*, 0.936. This compound could be precipitated INC WYINTHROP CHEMICAL COMPANY, by hydrogen chloride fiom ethanol solution aa its hydroRENSSELAER, NEWYORK J O H N A . KIVC chloride, m. p. 193-195 The amine was analyzed. RECEIVLD OCTOBER 4, 1945 Anal. Calcd. for CI~HIIOIN:C, 61.8; H, 11.6; neut. equiv., 233. Found: C, 61.7; H, 11.5; neut. equiv., 221. When the amine was treated with one equivalent of N-Furfurylmaleamic Acid and N,N-Furfuryhethylmalepicric acid in ethanol and crystallized from this medium, amic Acid a picrate m. p. 65-66' was formed. The following two derivatives were obtained by mixing Anal. Calcd. for C~fitoO~oNc: C, 46.75; H , 6.54. maleic anhydride with an equivalent amount of the corresponding amine in ether. Considerable heat was evolved Found: C, 47.0; H, 6.26. When two equivalents of picric acid were used, the comin both instances, with the products precipitating almost pound 2 picric acid: l,p',~,",9"'-triethoxytriethylamine immediately. N-Furfurylmaleamic Acid.-Seven grams of furfuryl- was formed, m. p. 229" after crystallization frem alcohol. amine gave 10 g. of white plates, m. p. 114' (uncor.), reAnal. Calcd. for GrHIrOl,Nr: C, 41.7; H, 4.82. crystallized first from an alcohol-ether mixture, and then Found: C, 42.0; H, 5.09. from alcohol. The crystals are soluble in alcohol, water, DEPARTMENT OF CHEMISTRY ethyl acetate and acetone, insoluble in ether. UNIVERSITY OF TORONTO H.H. RICHMOND Anal. Calcd. for CIHoOdN: C, 55.33; H, 4.62; neut. TORONTO, ONTARIO, CANADA GEORGE F. WRIGHT equiv., 195. Found: C, 55.38; H, 4.59; neut. equiv., RECEIVED SEPTEMBER 7, 1945 192. N,N-Furfurylmethylmaleamk Acid.-Five grams of furfurylmethylamine gave 5 g. of white product, m. p. 172173' (uncor.), recrystallized twice from a mixture of alco- DL(trimethylsily1) Sulfate and Lead Trimethylsilanolate hol and ether, soluble in alcohol, ethyl acetate, water, Di-(trimetfiylsilyl) sulfate has been prepared by the acetone and methanol, insoluble in ether. reaction Anal. Calcd. for C I ~ H I I O ~ N C,: 57.42; €1, 5.26; neut. 2(CHI)&iC1 H,SOb --3 [(CHI)~Si]&O, 2HC1 equiv., 209. Found: C, 57.43;H, 5.29; neut. equiv., 206. It is a white crystalline solid, easily hydrolyzed by water CHEMISTRY LABORATORY to hexarnethyldisiloxane and sulfuric acid. The correUNIVERSITY OF COLORADO chloride' and phosphate' are liquids, likewise BOULDER, COLORADO WERNERHERZ sponding easily hydrolyzable. R ~ c s r v r mSEPTEMBER 27, 1945 Lead trimethylsilanolate has been prepared by the reaction (CH1):SiOH p',,9",p"'-Triethoxytriethylamine~ PbO +[(CHa)sSiO]gPb H 2 0 This non-toxic compound resulted instead of trivinyl- It is a white crystalline solid, soluble in organic solvents, amine by heating a solution of 6.24 g. (0.111 mole) of potas- and is easily hydrolyzed by dilute sulfuric acid. Di-(trirnethylsilyl) Sulfate.-Nine and eight-tenths sium hydroxide in 25 cc. 95%. ethanol, under reflux, with 4.43 g. (0.01R3 mole) of trichlorotriethylaniine hydro- grams of sulfuric acid was added dropwise to 23.8 g. of (CHJISiCI with violent shaking. Hydrogen chloride was
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(1) Thia compound is mentioned in French Patent 711,560(1931), but no dewription of its preparation or properties is recorded. The compound aIso is incorrectly indexed in C. A . , 31, 10, f . ' l (1037). user the reference contoins no mention of it.
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+
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(1) A. G. Taylor and B. V. dG. Walden, T€UlJOURNAL, 66, 842 (1944); W. F. Gillism and R.0.S u e r , ibid., S6, 1793 (1944). (2) R. 0.Sauer. ibid.. 66, 1707 (1944).
